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Updated: May 8, 2026

Retropinacol/Cross-pinacol Coupling Reactions - A Catalytic Access to 1,2-Unsymmetrical Diols
Published on: April 4, 2014
Reaction of benzopinacol with non-ionic bases: reversing the pinacol coupling
Michal Zalibera1, Peter Nesvadba, Georg Gescheidt
1Institute of Physical and Theoretical Chemistry, Graz University of Technology , Stremayrgasse 9, 8010 Graz, Austria , and BASF Schweiz AG , 4002 Basel, Switzerland.
Abstract:
The reaction of benzopinacol with the non-ionic bases butyllithium and phosphazene P4 leads to the formation of the corresponding ketyl radical anions, which have been characterized by EPR/ENDOR spectroscopy. This conversion has a high efficiency. Such a reversed pinacol reaction can be used for a controlled release of ketyl radicals. Moreover, the nature of the base has a marked effect on the association of the ketyl radical anion and the counterions. This illustrates the importance of ion pairing for reductive coupling.
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